Hydroxypropyl cellulose liquid hair preparation



United States Patent 3,210,251 HYDROXYPRO'PYL C-ELLULOSE LIQUID HAIR PREPARATION Eugene D. Klug, Wilmington, Del., assignor to Hercules Powder Company, Wilmington, Del., a corporation of Delaware No Drawing. Filed Feb. 8, 1963, Ser. No. 257,063 '9 Claims. (Cl. 16787) The present invention relates to hair dressing compositions (sometimes called hair preparations) for application to the surface of hair in order to retain it in place and to give it a natural luster.

One type of hair preparation Within the scope of the present invention is referred to in the art as hair sprays, and this invention will be described in part with reference to hair sprays. By so doing however, applicant does not intend to limit his invention to hair preparations which are sprayable. The hair preparations of the present invention may be applied in a number of ways in addition to spraying, e.g., by brushing, combing, hand massaging, and the like. Unless the hair preparations are to be sprayed, they need no propellant.

A representative hair preparation to which the present invention is directed, although not limited thereto, is the aerosol type hair spray containing a pressure-generating material (often called a propellant) as an atomizing or spraying aid. Such hair sprays consists mainly of a filmforming material, a nontoxic liquid and a propellant. Usually the nontoxic liquid is a solvent (and in many cases an organic solvent) for the film-forming material. Likewise, often the film-forming material appears in solution in the solvent-propellant mixture.

Hair preparations have an entirely different function and purpose from that of permanent wave compositions and are clearly distinguishable thereover. More specifically, permanent wave compositions are almost invariably water solutions or suspensions of materials which are brushed or combed into the hair, often while the hair is curled, set and otherwise dressed, and upon drying the hair assumes a more or less permanent set and style dress. The drying process to develop the permanent set requires a relatively long period of time. Hair preparations, on the other hand, are intended for application (often by spraying from an aerosol-type container) to the outer strands of hair, after the hair has been permanently waved, brushed, combed, or otherwise dressed, to retain the hair in its previously dressed condition. Such hair preparations provide a substantially invisible hair net which holds the locks and outer strands of hair together, and thus enhance and preserve the dressed condition of the hair. Also, contrary to the use of hair preparations of the present invention, the use of permanent wave formulations generally involves .a chemical modification of the hair.

To serve their purpose efiectively, hair preparations must be very fast evaporating in contrast to permanent wave compositions and must have good adhesion to human hair without imparting stickiness or brittleness thereto. They should enhance the natural sheen of the hair, rather than have a dulling effect, and they should be easily removed from the hair upon normal washing or shampooing. Moreover, they should be readily sprayable from the usual aerosol-type containers without clogging the valve of the container. It is apparent, therefore, that a hair preparation must meet a rather exacting combination of requirements to be considered satisfactory.

As might be expected it is highly desirable that the film former have very good film-forming properties. The film former should readily form a film which is pliable or flexible. The film should be transparent and should not flake. The film should be relatively nonsticky even at high rela- Patented Oct. 5, 1965 tive humidity and and yet it should have sufiicient tack to stay on the hair for the desired period of time. In addition, the film-forming material should be soluble in water as well as in polar organic solvents, and yet its equilibrium moisture content value should be low in order to avoid the development of stickness in the hair.

It has been found in accordance with the present invention that excellent hair preparations are provided by compositions comprising a particular and novel hydroxypropyl cellulose, a nontoxic liquid, and a propellant if desired. Preferably the nontoxic liquid is an organic solvent for the hydroxypropyl cellulose. Preferably the mixture of the nontoxic liquid and propellant will also be a solvent for the hydroxypropyl cellulose. If the hydroxypropyl cellulose is not in solution in the final hair praparation composition, it should be in dispersion therein for best resutls. The novel hydroxypropyl cellulose products used in the present invention and the novel process of making said products are described and claimed in copending application Serial No. 257,064 entitled, Hydroxypropyl Cellulose and Process, filed on even date herewith in the name of Eugene D. Klug as inventor.

The purpose of the following two paragraphs is to explain the use herein and in the prior art of the terms degree of substitution (D.S.) and MS.

There are three hydroxyl groups in each anhydroglucose unit in the cellulose molecule. D.S. is the average number of hydroxyl groups substituted in the cellulose per anhydroglucose unit. MS. is the average number of moles of reactant combined with the cellulose per anhydroglucose unit. For the alkyl, carboxyalkyl, or acyl derivatives of cellulose, the D8. and M.S. are the same. For the hydroxyalkyl derivatives of cellulose, the MS. is generally greater than the D5. The reason for this is that each time a hydroxyalkyl group is introduced into the cellulose molecule, an additional hydroxyl group is formed which itself is capable of hydroxyalkylation. As a result of this, side chains of considerable length may form on the cellulose molecule. The M.S./D.S. ratio represents the average length of these side chains. Thus, from the foregoing it will be seen that the D8. of a cellulose derivative can be no higher than 3, whereas the MS. may be considerably higher than 3, depending on the extent to which side chains are formed.

The two most widely used methods for determining M.S. are the Zeisel-Morgan method and the terminal methyl method. The Zeisel-Morgan method is reported beginning at page 500, Vol. 18, 1946 of Industrial and Engineering Chemistry, Analytical Edition. The terminal methyl method is reported by Lemieux and Purves beginning at page 485, Vol. 25B, 1947, of Canadian Journal of Research. Some are of the opinion that perhaps the latter method is somewhat more accurate. However all those skilled in the art realize that it is quite difiicult to obtain a high degree of accuracy in determing M.S. at high M.S. levels, and that the accuracy of neither of these methods is as high as desired. All of the MS. values given herein were determined by the terminal methyl method. This explanation is being given in order to make it clear that although the MS. values herein may not be highly accurate, they were determined by the most accurate method known.

All viscosities given herein were determined with a standard Brook-field Synchro-Lectric LVF viscometer using an aqueous solution, unless otherwise indicated, of the hydroxypropyl cellulose of the concentration specified and at a temperature of 25 C.

The following examples illustrate the present invention, but they are not intended to limit the present invention beyond the scope of the appended claims.

Two methods are commonly practiced in loading aerosol containers, namely cold-loading and pressure-loading. Pressure-loading was used in the following Examples 1 and 2. In the following examples a solution of all the ingredients of the desired hair spray composition, except the propellant, were placed in an aerosol container at room temperature, the container was closed with an aerosol-type valve, the propellant was metered in under pressure through the valve by buret, and finally a spray head was attached to the container.

EXAMPLE 1 A hair spray formulation was prepared containing the constituents set forth in Table 1 below. Unless otherwise indicated, the percentages and parts given in the examples and elsewhere herein are by weight of the total hair spray formulation.

200 grams of the formulation in Table 1 above was placed in an aerosol-type container and successfully used on a number of subjects.

EXAMPLE 2 Additional hair spray formulations were prepared and packaged, duplicating Example 1 above except that a different hydroxypropyl cellulose product of the present invention was used. These hair spray formulations also were successfully used on a number of subjects.

The hydroxypropyl cellulose products used in Examples 1 and 2 above had the following properties:

Example No 1 2 M.S 2.80 3. 28 Solution concentration (percent by volume) 2 5 Viscosity (cps) in water 12. 5 240 Viscosity (cps) in absolute ethanol 175 EXAMPLE 3 A hair preparation formulation was prepared by mixing together the constituents set forth in Table 2 below.

Table 2 Constituent: Amount, parts Hydroxypropyl cellulose 1.0 Glycerol 1.5 Absolute ethanol 20.0

Water 25.0

The hydroxypropyl cellulose had an M.S. of 3.31 and a 2% aqueous solution viscosity of 100 cps. The viscosity of the hair preparation formulation was 240 cps. This hair preparation formulation was applied to the hair by spreading on the hand and rubbing into the hair. It dried quickly and did not impart stickiness nor flake. It was very beneficial in grooming the hair and keeping it in place.

As those skilled in this art will appreciate, many variations may be made in the above conditions Within the scope of this invention defined in the appended claims.

Although it is preferred to use a plasticizer in the hair spray composition of the present invention, this is not necessary. If a plasticizer is desired, the art is well aware of many such suitable materials. Likewise the art knows that in most cases it is preferable that the plasticizer used will be in solution or at least in suspension in the organic solvent-propellant mixture. Typical examples of suitable plasticizers include the glycols, e..g., propylene glycol, diand tripropylene glycol, dimethyl phthalate; trimethylolpropane; lanolin; glycerol and its water-soluble esters such as, e.g., mono-, di-, and triacetin. The amount of plasticizer, based on the weight of the hydroxypropyl cellulose, may vary from 0% to 100%, but preferably will be about l0%80%.

There are a number of nontoxic liquids which are suitable for the present invention. These include, e.g., water, ethyl acetate, and the lower aliphatic saturated alcohols such as, e..g., ethyl alcohol and isopropyl alcohol.

Usually the amount of solvent by Weight of the total hair preparation composition will be about l0%-60% and preferably about 25 %40%.

One may use in the present invention one or more of the many known aerosol propellants. The trade has divided these propellants into three general classes. These include, e.g., compressed gases, liquified hydrocarbons, and fiuorinated hydrocarbons. The more Widely used compressed gases include CO N 0 and N The more Widely used liquid hydrocarbons include, e..g., propane, N-butane, and isobutane. The fluorinated hydrocarbon aerosol propellants are known in the trade as the Freon-s." The most widely used Freons include, e.g., dichlorodilluoromethane (Freon 12), trichl-oromon-ofluoromethane (Freon ll), dichlorotet-rafluoroethane (Freon 114) and octofluorocyclobutane (Freon (3-3-18).

The amount of propellant may vary considerably but usually will .be about 25 by weight of the total hair spray composition, preferably about 50%-70%.

Generally the amount of hydroxypropyl cellulose will be about 1%-6%, preferably about 2%-3%, by weight of the total hair preparation composition. The minimum M.S. of the hydroxypropyl cellulose is critical and must be at least 2.5, preferably 3-10, 3.55 being specifically preferred. Although the viscosity of the hydroxypropyl cellulose is not critical, it is important but may vary over quite a wide range. A 2% solution viscosity of 500 cps. and below is preferred, although somewhat higher visco'sities can be used. Quite low viscosities may be employed, e.g., a 5% solution viscosity as low as 25 cps. is operable.

Usually the hair preparation compositions will be in the form of a single-phase system; however, Where water is used as the nontoxic liquid and some of the other constituents are immiscible with water, the hair preparation compositions will be in the form of a two-phase system, namely a phase which is primarily aqueous and another phase which is primarily nonaqueous. In using hair spray compositions comprising a two-phase system, the constituents become properly mixed during spraying and before they contact the hair.

One unexpected and very useful property of the hydroxypropyl cellulose used in the present invention is that it is soluble in many polar organic solvents. By the statement herein that said hydroxypropyl cellulose is soluble in polar organic solvents is meant that it is more soluble if at least one polar organic solvent is present. Thus, the hydroxypropyl cellulose is soluble in a mixture of polar and nonpolar organic solvents such as a mixture, e.g., of a lower aliphatic alcohol and acetone, Z-ethoxy-ethanol-l, or ethyl acetate.

As many apparent and Widely different embodiments of this invention may be made without departing from the spirit and scope thereof, it is to be understood that the invention is not limited to the specific embodiments thereof except as defined in the appended claims.

What I claim and desire to protect by Letters Patent is:

l. A liquid hair preparation comprising hydroxypropyl cellulose, a nontoxic liquid and a plasticizer, said bydroxypropyl cellulose being characterized by (1) forming films which are transparent, pliable and of good tensile strength, (2) being soluble in cold water and in polar organic solvents, (3) having an M.S. of 25-40 and a viscosity .at 25 C. of 25 cps. to 500 cps. in a 5% and 2% aqueous solution, respectively, the amount of said hy- 5 droxyp-rPyl Cellulose, nontoxic liquid and plasticizer 'being l%6%, 10%-60% and 10%-100%, respectively by weight of said hair preparation.

2. A liquid hair preparation comprising hydroxypropyl cellulose, a nontoxic liquid and a propellant, said hydroxypropyl cellulose being characterized by (1) forming films which are transparent, pliable, and which do not flake, (2) being soluble in cold Water and in polar organic solvents, (3) having an MS. of 3.5-5 and a viscosity at 25 C. of 25 cps-500 cps. in a 5% and 2% aqueous solution, respectively, the amount of said hydroxypropyl cellulose, nontoxic liquid and propellant being 1%6%, %-60% and %-85%, respectively, by Weight of said hair preparation.

3. A liquid hair preparation comprising hydroxypropyl cellulose, a nontoxic liquid, a propellant and a plasticizer, said hydroxypropyl cellulose being characterized by (1) forming films which are transparent, pliable, and of .good tensile strength, (2) being soluble in cold Water and in polar organic solvents, (3) having an MS. of 3.5-5 and a viscosity at 25 C. of 25 cps-500 cps. in a 5% and 2% aqueous solution, respectively, the amount of said hydroxypropyl cellulose, nontoxic liquid, propellant and plasticizer being 1%-6%, 10%-60%, 25%-85% and 10%-100%, respectively, by weight of said hair preparation.

4. Product of claim 1 wherein the plasticizer is a glycol.

5. Product of claim 1 wherein the plasticzer is glycerin.

References Cited by the Examiner UNITED STATES PATENTS 2,362,761 11/44 Med-1 16787.1 2,840,485 6/58 Greminger et al 167-63 2,857,314 10/58 Philips 16787 2,957,838 lO/60 Mills 167-87.1

OTHER REFERENCES Sagarin, Cosmetics, Science and Technology, In-terscience Publishers, New York, N.Y. (1957), pp. 803-817.

Proceedings, th Mid-year Meeting CSMA, May 24- 25, 1954, pp. 23-24.

JULIAN S. LEVIT'I, Primary Examiner.

FRANK CACCIAPAGLIA, Examiner. 

1. A LIQUID HAIR PREPARATION COMPRISING HYDROXYPROPYL CELLULOSE, A NONTOXIC LIQUID AND A PLASTICIZER, SAID HYDROXYPROPYL CELLULOSE BEING CHARACTERIZED BY (1) FORMING FIRMS WHICH ARE TRANSPARENT, PLIABLE AND OF GOOD TENSILE STRENGTH, (2) BEING SOLUBLE IN COLD WATER AND IN POLAR ORGANIC SOLVENTS, (3) HAVING AN M.S. OF 2.5-10 AND A VISCOSITY AT 25*C. OF 25 CPS. TO 500 CPS. IN A 5% AND 2% AQUEOUS SOLUTION, RESPECTIVELY, THE AMOUNT OF SAID HYDROXYPROPYL CELLULOSE, NONTOXIC LIQUID AND PLASTICIZER BEING 1%-6%, 10%-60% AND 10%-100%, RESPECTIVELY BY WEIGHT OF SAID HAIR PREPARATION. 